JP2003165926A - Method for producing sulfonated solid particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for sulfonating the surface of pigment particles under mild conditions without using a solvent, wherein the reaction is easily controlled, and a to obtain the sulfonated pigment. <P>SOLUTION: The method for producing sulfonated solid particles is characterized in that a dry powder and/or granular solid particles are sulfonated by using sulfur trioxide gas obtained through catalytic oxidation of sulfur dioxide gas produced by burning sulfur, in a state in which they are in gas- and solid- phases. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing sulfonated solid particles, sulfonated solid particles and a composition thereof. More specifically, the present invention relates to a method for producing sulfonated solid particles, a method for producing sulfonated solid particles, in which sulfur trioxide gas obtained by catalytically oxidizing a sulfur dioxide gas produced by burning sulfur, is reacted with the sulfonated solid particles, and uses thereof.

[0002]

2. Description of the Related Art Conventionally, water-soluble dyes have mainly been used as water-soluble colorants. Felt-tip pen, fiber pen,
As an ink for writing instruments such as ballpoint pens, there is a tendency to use an aqueous pigment dispersion from an aqueous dye solution. On the other hand, water-based inks using a water-soluble dye as a colorant have been mainly used for inkjet inks.

However, the above dye ink has a drawback that it is inferior in fastness such as light resistance and water resistance. Therefore, instead of the water-soluble dye, a pigment ink using a pigment having excellent physical properties such as light resistance and water resistance has been studied, and an inkjet printer using the pigment ink has been put into practical use. . In addition, as a colorant for paints and gravure inks, the use of an aqueous colorant that hardly uses an organic solvent is increasing from the viewpoint of environmental importance.

As described above, when the pigment is used for applications such as water-based inks, the fineness of the pigment improves the sharpness, dullness and transparency of the hue of the pigment. However, the finely divided pigment is uniformly dispersed in an aqueous medium,
Further, a dispersant is necessary to secure the storage stability of the dispersion, but it is difficult to secure the long-term stability of the pigment dispersion only with the dispersant. As an improvement, it has been studied and proposed to introduce a sulfone group or a carboxylic acid group into the surface of the pigment to modify the surface of the pigment.

Generally, an organic pigment has a weak surface polarity and cannot sufficiently adsorb a resin dispersant in a vehicle on the surface of the pigment due to a hydrogen bond or the like. Therefore, dispersion stability of the pigment in a dispersion medium is insufficient. is there. Therefore, a pigment derivative in which a group having a compatibility with the resin dispersant in the vehicle or a polar group is bound to the pigment in advance is adsorbed on the surface of the pigment to enhance the affinity between the pigment and the resin dispersant, and the dispersion medium Methods have been taken to improve the dispersion stability of pigments therein. For example, Japanese Patent No. 1,241,792 proposes a pigment dispersion liquid in which a resin dispersant and a fluidizing agent having an ammonium sulfonate group are added to the pigment.

Also in the colorant for a color filter (hereinafter abbreviated as "CF"), it is important to miniaturize the pigment in order to improve the transparency, image clarity and transmittance of the CF formed. Is. Particularly in the case of a CF colorant, it is important to secure the fluidity of the pigment dispersion, the prevention of aggregation of the pigment, and the storage stability. For that purpose, the above-mentioned pigment derivative or pigment dispersant is used.

[0007]

[Problems to be Solved by the Invention] Under these circumstances,
Various methods for imparting a polar group to a pigment have been studied, and in recent years, a method for introducing a polar group into a pigment by a sulfonation method that does not use sulfuric acid or fuming sulfuric acid, which has been a conventional method, has been proposed. There is. This method is a method in which a sulfonating agent that is solid at room temperature is used alone in a solvent or without using a solvent, and in order to uniformly perform sulfonation on the surface of the pigment, the pigment is finely dispersed before sulfonation. Pretreatment is required. Furthermore, in sulfonation in a solvent, after sulfonation,
Separation of sulfonated pigment and solvent, recovery and purification of solvent,
This is an economically disadvantageous method because it requires a neutralization treatment of a large amount of sulfonating agent which becomes waste acid.

Further, a method of mixing a sulfonating agent which is solid at room temperature (for example, amidosulfuric acid, sulfur trioxide pyridine complex, sulfur trioxide dimethylformamide complex, etc.) with a pigment and heat sulfonation is carried out at a sulfonation temperature of Care must be taken because the morphology of the reaction system differs depending on whether it is above or below the melting point of the sulfonating agent. That is, a relatively high sulfonation temperature (for example, 150 to 210 ° C.) is required, and it is not easy to control the sulfonation such as setting the sulfonation time.

There is also a method in which solid sulfur trioxide is heated and vaporized in a laboratory apparatus using a flask to generate sulfur trioxide gas, and the carbon powder is sulfonated. The solid sulfur trioxide used in this method is a strongly acidic and strongly oxidative compound that is highly toxic and may cause various irritation to the mucous membranes of workers and chemical injury to the skin. When touched, it absorbs water to produce white smoke, when it comes into contact with water, it explosively acts and dissolves in water to form sulfuric acid. There is.

The present inventors have studied to develop a method capable of easily controlling sulfonation under a mild condition without using a solvent, and particularly capable of industrially producing a large amount of sulfonated solid particles. Using sulfur trioxide gas obtained by catalytically oxidizing sulfur dioxide gas produced by burning,
It has been found that the above problems can be solved by sulfonation of solid particles, and the present invention has been completed.

The term "solid particles" as used herein means organic pigments, carbon black pigments, conductive carbon blacks, carbon blacks for batteries, carbon blacks for rubbers (in the present specification, the above various carbon blacks are collectively referred to as "carbon black fine particles"). In some cases), a substance capable of sulfonation on the particle surface such as a water-insoluble dye or resin fine particles. Further, the shape thereof may be any shape such as powder, granule, granule, flake, fibril and the like (referred to as “powder and / or granule” in the present specification).

[0012]

DISCLOSURE OF THE INVENTION The present invention relates to a sulfur trioxide gas obtained by catalytically oxidizing a sulfur dioxide gas produced by burning sulfur with dry powder and / or granular solid particles. The present invention provides a method for producing sulfonated solid particles, which comprises sulfonation in a gas-solid state, a sulfonated solid particle, a (colored) composition containing the particle, and use thereof.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. In the present invention, the solid particles to be sulfonated are organic pigments, carbon black fine particles, water-insoluble dyes, resin fine particles and the like. First, all known organic pigments are targeted as organic pigments, specifically, soluble / insoluble azo pigments, polymer azo pigments, methine / azomethine pigments, azomethine azo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments,
Examples include isoindolinone pigments, isoindoline pigments, ansanthuron pigments, perinone pigments, perylene pigments, anthraquinone pigments, quinophthalone pigments, indigo / thioindigo pigments, dioxazine pigments, quinacridone pigments, and metal complex pigments.

As the carbon black fine particles, first,
Examples include carbon black pigments for coloring. Carbon black fine particles other than those for coloring include carbon black for batteries, conductive carbon black, carbon black for rubber, and the like, specifically, acetylene black, thermal black, furnace black, lamp black, channel black, roll black and the like. .

The average particle size of the sulfonated pigments, including carbon black pigments for coloring, is the same as the particle size of pigments conventionally used in various applications. For example, sulfonated pigments are usually When it is used as a coloring agent for printing inks and paints, the particle size of the pigment marketed as a product may be used. However, when a sulfonated pigment is used for a CF colorant and an inkjet ink, it is preferable to use a pigment having the following particle size. That is, in the case of the CF colorant, the average particle size is preferably 0.01 to 0.5 μm, and more preferably 0.02 to 0.2 μm. In the case of a colorant for inkjet ink, a preferable average particle size is 0.01 to 0.
5 μm, more preferably 0.02 to 0.2 μm
Is.

The method for producing sulfonated solid particles of the present invention comprises drying solid particles such as pigments and sulfur trioxide gas obtained by catalytically oxidizing sulfur dioxide gas produced by burning sulfur. Directly sulfonation the solid particles by bringing them into direct contact with each other in a gas phase-solid phase and preferably used as a mixed gas with a pigment such as air, nitrogen gas, argon gas and a gas inert to sulfur trioxide. It is a feature. As an aspect of the sulfonation, a mixed gas of the above-mentioned inert gas and sulfur trioxide gas is introduced into the reaction system rather than a method of directly introducing the sulfur trioxide gas into the reaction system in which dried solid particles are present. The method is preferable because the sulfonation can be easily controlled.

In the sulfonation of any embodiment of the method of the present invention, the sulfonation temperature is preferably 80-13.
The temperature is 0 ° C, more preferably 100 to 110 ° C. When the mixed gas is used as described above, the concentration of the sulfur trioxide gas in the mixed gas varies depending on the type of the pigment to be sulfonated, the particle size, the desired degree of sulfonation, etc., and cannot be specified unconditionally. Although a preliminary examination of
Usually, it is about 1 to 20% by mass. The sulfonation time also varies depending on the sulfonation temperature, the degree of sulfonation, the concentration of sulfur trioxide in the reaction system, and the like, and cannot be specified unconditionally, but is usually 0.5 to 6 hours, preferably 1 to 3 hours. is there.

The amount of sulfone groups (—SO ₃ H) introduced on the surface of solid particles in the method of the present invention will be described. In the method of the present invention, the sulfur trioxide gas obtained by catalytically oxidizing the sulfur dioxide gas produced by burning sulfur is used as it is or in the presence of an inert gas mixed for the sulfonation. It is possible to increase the rate,
By controlling the sulfonation conditions, a very wide range of sulfonation rates can be obtained, but especially high introduction of sulfo groups into individual molecules of individual solid particles or individual particles, that is, high degree of sulfonation can be achieved. Is.

In carbon black pigments, conductive carbon blacks, battery carbon blacks, rubber carbon blacks, etc., sulfone groups are introduced into the aromatic nuclei on the surface of individual solid particles, and the degree of sulfonation is the unit of carbon black. About 1 to 10% by weight, preferably about 3% by weight
~ 6% by mass. Further, in organic pigments, water-insoluble dyes, resin fine particles and the like, a sulfone group may be introduced on the surface of those solid particles, or a sulfone group may be introduced in the molecular structure of each solid particle. Therefore, the degree of sulfonation is usually about 0.1 to 30% by mass, preferably about 0.5 to 10% by mass, based on the unit mass of the pigment, although it varies depending on the type and chemical structure of the pigment.

If the introduction amount of the sulfone group is too small, the polarity of the solid particles, for example, the obtained sulfonated pigment is insufficient, and the good dispersion stability in an aqueous or oily medium,
Storage stability cannot be obtained. On the other hand, if the amount of the sulfone group is too large, the solid particles, particularly various fastnesses and physical properties as a pigment are deteriorated. In addition, the pigment with a small introduction amount of sulfone group,
It can be used as it is as an ordinary pigment. On the other hand, a pigment in which at least one sulfone group is introduced into one molecule of the pigment molecule (the amount of the sulfone group is about 10 to 30% by mass relative to the pigment unit mass) can be used as a pigment as it is. It can also be used as a so-called pigment derivative (pigment dispersant / dispersion aid), which is preferably used in combination with a pigment.

The sulfonated pigment obtained by the method of the present invention is more effectively used in an aqueous medium and an oil medium by neutralizing the sulfone group with a basic compound to form a salt group. . When the sulfonated pigment is used in an aqueous dispersion medium, the sulfone group may be used in the form of a free sulfone group or a salt with sodium, potassium, calcium, ammonium, amines, alkanolamines and the like. it can. On the other hand, when the sulfonated pigment is used in an oily dispersion medium, an oligomer or a resin, the above-mentioned free sulfone group, metal salt or organic amine salt may be used, but a hydrocarbon group having 6 or more carbon atoms, For example,
Salts of primary, secondary, and tertiary amines or quaternary ammonium salts having an alkyl group, a cycloalkyl group, or an aryl group, and salts neutralized with a known basic compound such as polyamine or a polyester oligomer derivative of polyethyleneimine. Can be used in the form of.

Examples of the above amines include dimethylamine, trimethylamine, diethylamine, triethylamine, n-propylamine, isopropylamine, n-butylamine, t-butylamine, hexylamine, laurylamine, stearylamine, oleylamine, 1, Aliphatic amines such as 2-dimethylpropylamine and stearylaminopropylamine; hydroxyethylamine, hydroxypropylamine, N, N-dimethylaminoethanolamine, N, N-diethylaminoethanolamine, N, N-dimethylaminopropanolamine, N , N-diethylaminopropanolamine and other alkanolamines; cyclohexylamine,
Alicyclic amines such as pyridine, piperidine, piperazine and morpholine; aromatic amines such as aniline and aniline derivatives can be mentioned. Examples of the quaternary ammonium compound include a methyl distearyl ammonium compound and a trimethyl stearyl ammonium compound.

The post-treatment of the pigment after sulfonation will be described in comparison with the case of using sulfuric acid as a sulfonating agent and neutralizing the waste sulfuric acid after sulfonation. For example, when the copper phthalocyanine pigment that is usually used is sulfonated with sulfuric acid, sulfuric acid is used in an amount of about 10 times the mass of the pigment. On the other hand, in the method of the present invention, for example, in Example 1 described later, sulfonated carbon black obtained by sulfonation of 100 parts by mass of granular carbon black pigment with a mixed gas of sulfur trioxide gas and air is added to ion-exchanged water. It was charged, stirred, filtered, and washed with water until the pH became constant. Sodium hydroxide required for neutralization of these filtrates and water was 16.
It was 9 parts by mass. This is 2 per 100 parts by weight of pigment
Only 0.7 parts by weight of sulfuric acid were used in excess. As described above, the amount of the sulfonating agent (sulfur trioxide) used in the present invention is significantly smaller than that in the usual sulfonation method using sulfuric acid, and not only the wastewater treatment load but also the work process and the economy are reduced. This is also a great advantage.

The sulfonated pigment obtained according to the present invention may be prepared by dispersing it alone in a medium to give a coloring composition, or by adding the sulfonated pigment to another pigment (non-sulfonated pigment). There is a coloring composition which is contained as a dispersant (dispersion aid) for other pigments, and various dispersion media, for example, water, water-hydrophilic organic solvent mixed media, organic solvents, oils and fats, plasticizers, depending on the application. The sulfonated pigment may be finely dispersed and used in the agent, oligomer or resin. Examples of the method for finely dispersing the sulfonated pigment in the medium include, for example, a ball mill, a sand mill, an attritor, a horizontal continuous medium disperser, a vertical continuous medium disperser, a pin mill, a triple roll, a pressure kneader, a tumbler, and a Henschel mixer. , Hammer mill, Banbury mixer, extruder, etc.

The sulfonated pigment obtained in the present invention is a colorant for paints, printing inks, ink jet inks, stationery inks, CF colorants, resin colorants, or ordinary pigments (not sulfonated). It can be used as a dispersant (dispersion aid) for pigments.

The paint using the sulfonated pigment obtained in the present invention as a colorant includes all paints using conventionally known pigments and is not particularly limited. For example,
Automotive paint, architectural paint, wood paint, vehicle / equipment paint, household paint, plastic paint, precoat metal paint, can paint, marine paint, anticorrosion paint, photocurable paint, electron beam curable paint, Examples include electrostatic powder paints and vinyl sol paints.

The printing ink includes all conventionally known printing inks and is not particularly limited. Examples thereof include letterpress ink, planographic ink, gravure ink, screen ink, newspaper ink, flexo ink and the like.

The paints and printing inks as described above may be solid or liquid, and in the case of liquid, water or a water-hydrophilic organic solvent mixture or an organic solvent is used, and the organic solvent is a fat. Group hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, esters,
Ketones, glycol ethers, alcohols, etc. are used, and are not particularly limited.

As the vehicle of the paint or the printing ink, a conventionally known oily or aqueous vehicle is used according to each application. Examples of the resin of the vehicle include alkyd resin, aminoalkyd resin and baking acrylic resin. , Acrylic lacquer resin, polyester resin, epoxy resin, butylated melamine resin, methylated melamine resin, rosin-modified phenol resin, polyurethane resin, styrene resin, styrene acrylic resin, styrene-diene copolymer, vinyl chloride copolymer, acetic acid Examples thereof include vinyl resins, vinyl acetate copolymers, ethylene-vinyl acetate resins, butyral resins, drying oils and boil oils.

The resin colored with the sulfonated pigment obtained in the present invention includes polyethylene resin, polypropylene resin, polyvinyl chloride resin, styrene resin, acrylonitrile / styrene resin, polyester resin, acrylic resin, methacryl-styrene resin. , ABS resin and the like.

The coloring composition of the present invention is used as an image display material in an image display method, and is also used as an image recording agent such as an inkjet ink or an electrodeposition recording liquid in an inkjet recording method or an electrodeposition recording method, respectively. Used for image recording method.

First, as a typical example of the use of the coloring composition,
The inkjet ink will be described in more detail.
Inkjet ink is composed of a colorant, a dispersant that is a water-soluble resin in addition to water, a surfactant, a water-based resin fixing agent, an organic solvent, etc., and is intended to improve the storage stability and ejection stability of the ink. Then, a surface tension adjusting agent, a viscosity adjusting agent, a specific resistance adjusting agent, an antifoaming agent, an antifungal agent and the like can be added. The water used in this case is ion-exchanged water or ion-exchanged distilled water.

As the dispersant which is a water-soluble resin, for example, a resin such as an acrylic resin, an acrylic-styrene resin, a polyester resin, a polyamide resin or a polyurethane resin may be used alone or in combination. Examples of the dispersant which is an acrylic resin or an acrylic-styrene resin include (meth) acrylic acid ester- (meth) acrylic acid polymer, styrene- (meth) acrylic acid ester polymer, and styrene- (meth) acrylic acid ester. -(Meta)
Acrylic acid polymer, styrene-maleic acid ester-maleic acid polymer, isobutylene-maleic acid ester-
Maleic acid polymer). These water-soluble resin dispersants are usually used in an amount of
It is preferably used in the range of 10 to 50% by mass in consideration of the decrease in the storage stability and the ejection stability of the ink. Inorganic alkaline agents and organic alkaline agents such as ammonia and amines can be appropriately used as pH adjusters for these resins.

A surfactant may be added to the water-based ink for ink jet in order to improve the dispersibility of the pigment, the dispersion stability, the storage stability of the ink over time, or to adjust the surface tension. it can. Examples of the surfactant include anionic surfactants (alkyl sulfate ester salts, alkylaryl sulfonates, polyoxyethylene alkyl ether sulfonates, naphthalene sulfonic acid formalin condensates, etc.), nonionic surfactants ( Polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester, polyoxyethylene alkylamine ether, acetylene alcohols, acetylene glycols and the like can be used.

In addition, the water-based ink for ink jet,
A water-soluble organic solvent is usually used together with water in order to prevent the ink or the nozzle portion of the print head from drying and improve the ejection stability. Examples of the water-soluble organic solvent include polyhydric alcohols (ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, etc.), polyhydric alcohol ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc.), alcohols (methanol, ethanol). , Isopropyl alcohol, etc., amines (diethanolamine, ethanolamine, etc.), heterocycles (N
-Methyl-2-pyrrolidone, etc.), sulfolane, etc. are used.

Next, as another use of the coloring composition of the present invention, a CF dispersion liquid will be described. When preparing the dispersion, a pigment composition comprising a pigment having a desired hue and the sulfonated pigment obtained in the present invention is added to an organic solvent solution containing a suitable film-forming resin together with a dispersant for premixing, The pigment composition is dispersed. For example, a pigment composition and a dispersant are uniformly mixed and ground by a dispersion machine such as a vertical medium disperser, a horizontal medium disperser, or a ball mill, and a method of adding and mixing this in a liquid containing a film-forming resin, sulfuric acid. After dissolving the ordinary pigment and the sulfonated pigment obtained in the present invention in, etc., the sulfuric acid solution is precipitated in water, and both pigments are separated as a solid solution or a co-precipitate, and the obtained pigment composition is Similarly, the method of adding and mixing in a liquid containing a film-forming resin, a dispersant, etc. and grinding and dispersing can be mentioned.

In the present invention, as a liquid containing a film-forming resin for dispersing an ordinary pigment and the sulfonated pigment obtained in the present invention into a pigment dispersion, a conventionally known C is used.
The film-forming resin used in the F pigment dispersion is used. Moreover, an organic solvent, water, or a mixture of an organic solvent and water is used as the liquid medium. Further, conventionally known additives such as a dispersion aid, a smoothing agent, and an adhesion promoter can be added to the pigment dispersion liquid as needed.

The addition mass ratio of the pigment composition to the resin in the liquid containing the film-forming resin is preferably in the range of 5 parts by mass to 500 parts by mass with respect to 100 parts by mass of the film-forming resin. As the liquid containing the film forming resin, a liquid containing a photosensitive film forming resin or a liquid containing a non-photosensitive film forming resin is used. Examples of the liquid containing a photosensitive film-forming resin include liquids containing a photosensitive film-forming resin used in ultraviolet curable inks, electron beam curing inks and the like, and as liquids containing a non-photosensitive film-forming resin. Are varnishes used for printing inks such as letterpress inks, lithographic inks, gravure inks, screen inks, varnishes used for room temperature drying and baking paints, varnishes used for electrodeposition coating, varnishes used for thermal transfer ribbons, etc. Can be mentioned.

As the photosensitive film forming resin, a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polyacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, etc., and an unsaturated polyester resin, a polyester acrylate resin, Polyepoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin, polyol acrylate resin and the like,
Further, various monomers can be added as a reactive diluent.

Further, a photopolymerization initiator such as benzoin ether or benzophenone is added to a pigment dispersion containing a photosensitive resin, and the mixture is kneaded by a conventionally known method to obtain a photocurable photosensitive pigment dispersion. be able to. Also,
A thermosetting pigment dispersion can be prepared by using a thermal polymerization initiator instead of the above photopolymerization initiator.

Examples of the non-photosensitive film-forming resin include styrene- (meth) acrylic acid ester (co) polymer, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin,
A water-soluble salt of styrene-maleic acid ester copolymer,
Examples thereof include water-soluble salts of (meth) acrylic acid ester- (meth) acrylic acid copolymers and water-soluble amino polyester resins.

Carbon black other than for coloring can be sulfonated basically in the same manner as for coloring carbon black. In particular, conductive compositions such as conductive paints and conductive inks are used in the production of conductive materials such as antistatic films and wrapping paper for electronic parts with the development of electronic precision equipment. Conductive carbon blacks such as sulfonated acetylene blacks are useful.

The resin fine particles include polyolefin fine particles such as polypropylene.
Styrene: acrylonitrile: hydroxyethyl methacrylate: divinylbenzene (mass ratio 41.6:
7.1: 8.1: 8.7) Granules of cross-linked copolymer,
Examples thereof include granules of a styrene-divinylbenzene crosslinked copolymer used for an ion exchange resin and the like.

The method of the present invention as described above has the following advantages. 1) The shape of solid particles such as pigments is powder, granular, granular,
No matter what shape such as flakes or fibrils, sulfur trioxide can be contact-reacted on the surface of solid particles, so pretreatment such as fine dispersion of pigment particles to be sulfonated is unnecessary. Is.

2) Since the excess sulfur trioxide gas can be replaced with an inert gas such as air or nitrogen gas after the sulfonation, the sulfur trioxide adsorbed on the sulfonated pigment can be easily washed and neutralized. 3) Since solid particles such as pigments can be directly sulfonated with sulfur trioxide, sulfonation proceeds at low temperature, sulfonation can be easily controlled, and sulfonation efficiency is high. 4) Solid particles such as pigment particles are less likely to be destroyed.

5) For example, it is possible to sulfonate even solid particles such as a pigment which is susceptible to hydrolysis, which is hydrolyzed by sulfonation with sulfuric acid. 6) The excess sulfur trioxide gas recovered after sulfonation can be reused for other purposes. 7) Sulfur trioxide gas obtained by catalytically oxidizing sulfur dioxide gas produced by burning sulfur is used as a sulfonating agent. The control only needs to control the flow rate of the gas containing sulfur trioxide gas over the whole process, which makes it easy to manage the manufacturing process industrially, and there is little danger when handling a large amount of sulfur trioxide gas, and it is safe and easy. Sulfonates can be produced.

8) Since an organic solvent containing a sulfur trioxide complex, which requires a large amount of waste acid treatment and waste solvent treatment, is not used,
Waste liquid treatment is easy and economical. 9) In addition, carbon black produced by oxidation of hydrocarbons in particular has few positions for sulfonation, and it is difficult to introduce a sulfone group by the conventional method, but the method of the present invention directly reacts sulfur trioxide gas. Therefore, it is particularly excellent in introducing a sulfone group. As described above, the method of the present invention is a manufacturing method that is rational and easy to manufacture, and is economically advantageous.

[0048]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the text, “part” or “%” is based on mass unless otherwise specified.

Example 1 Powdery carbon black pigment (average particle size 0.013 μ
m) 100 parts of the product was pre-dried at 105 ° C. for 1 hour in a dryer, placed in a reaction vessel, and sulfur trioxide gas obtained by catalytically oxidizing sulfur dioxide gas produced by burning sulfur was adjusted to 80%. The mixture was heated to ˜110 ° C., introduced into the reaction vessel so as to have a concentration of 8% with respect to dry air, and sulfonated for 2 hours. Then, after cooling, the sulfonated carbon black was put into ion-exchanged water and stirred,
It was filtered and washed with water until the pH was constant. When these filtrates were neutralized with a 10% aqueous sodium hydroxide solution, 16.9 parts of pure sodium oxide was necessary. From this, the sulfur trioxide adsorbed on the sulfonated pigment was 20.7 parts in terms of sulfuric acid. Then, it was dried at 80 ° C. for 24 hours, and 103.4 parts of a surface-sulfonated carbon black pigment was obtained.

The carbon black pigment obtained was decomposed in a combustion flask, and sulfur in the pigment was quantified by ion chromatography. As a result, the resultant carbon black, contained 3.2% of a sulfone group (-SO ₃ H groups) with respect to the unit mass. When sulfonation was carried out in the same manner using the same granular material as the above carbon black, the sulfonated carbon black obtained had 3.1% sulfo groups (-
SO ₃ H group).

Example 2 A carbon black pigment was used as C.I. I. Pigment Red 12
2 (hereinafter, CI is omitted in the name of pigment)
A sulfonated pigment was obtained in the same manner as in Example 1 except that 100 parts (average particle size 0.1 μm) was used. The amount of sodium hydroxide required to neutralize the washing liquid after sulfonation was 24 parts, and from this, the amount of sulfur trioxide adsorbed on the sulfonated pigment was 29.4 parts in terms of sulfuric acid. Also, after drying, 104.5 parts of sulfonated pigment was obtained.
In this pigment, 3.9% of sulfonic groups were introduced per unit mass. This is a calculation in which about 0.15 sulfone groups were introduced per pigment molecule.

Examples 3 to 13 The yellow pigments, red pigments, blue pigments, purple pigments, and black pigments shown in Table 1 were sulfonated in the same manner as in Example 1. Table 1 shows the production results. For organic pigments other than carbon black pigments, the number of sulfone groups per pigment molecule is also shown.

[0053]

Examples 14 to 17 (Preparation and Evaluation of Inkjet Ink) The sulfonated carbon black pigment obtained in Example 1 was peptized in water and filtered to obtain an aqueous presscake (pigment solid content. 28%). 17.9 parts of the obtained sulfonated carbon black pigment aqueous press cake, 3 parts of a water-soluble acrylic resin dispersant, 14 parts of ethylene glycol, 6 parts of diethylene glycol, 20 parts of glycerin and 3 parts of water.
An aqueous pigment dispersion consisting of 9.1 parts was prepared and pigment coarse particles that could not be dispersed by an ultracentrifuge were removed to obtain a black aqueous ink for inkjet having an average particle diameter of the pigment of 72 nm.

Similarly, a pigment composition obtained by adding 0.8% of the sulfonated yellow pigment obtained in Example 4 to Pigment Yellow 74 (hereinafter referred to as "PY74-M"), the sulfone obtained in Example 2 Quinacridone red pigment and the sulfonated phthalocyanine blue pigment obtained in Example 10, respectively, and yellow aqueous ink for inkjet,
A red aqueous ink for inkjet and a blue aqueous ink for inkjet were obtained.

Each of the color water-based inks for ink jet obtained above was evaluated by the following methods. The average particle size of the pigment in the ink is determined by diluting each color ink with distilled water to a concentration specified by the measuring device, and then applying ultrasonic wave for 20 seconds to a test solution using a Coulter Submicron Particle Analyzer (Model Coulter Model). N-4). Each color ink diluted with water to a pigment concentration of 1% was used with a bar coater standard No. 4, and an RK control coater (Pr
It was developed by Int-Coat). The recording paper used for color development is Epson photo print paper 2.
The color measurement was performed using a CR-121 color difference meter manufactured by Minolta. The results are shown in Table 2.

[0057] An on-demand type inkjet printer having a piezo oscillator was used to perform four-color full-color printing using the yellow ink, blue ink, red ink, and black ink obtained above to obtain a clear full-color image.

Example 18 (Preparation of colorant for CF) Acrylic resin (methacrylic acid / butyl acrylate / styrene / hydroxyethyl acrylate = 25: 50:
Polymerized at a molar ratio of 15:10. Molecular weight 12,0
00, solid content 30%), Pigment Green-36
(Brominated phthalocyanine green), the pigment composition of Example 4 as a dispersant and a solvent (propylene glycol monomethyl ether acetate) (hereinafter abbreviated as PGMAc) were blended as shown in Table 3 below, and after premixing, a green color was obtained. Got the base color of.

Examples 19 and 20 Similarly, the brominated phthalocyanine green used in Example 18 was replaced with Pigment Blue 15: 6 (ε-type copper phthalocyanine blue) and the red pigment composition of Example 5, respectively. Blue and red base colors were obtained. The formulation is shown in Table 3.

[0060]

The base colors of Examples 18 to 20 were applied to a glass plate with a spin coater, dried and the maximum transmittance and maximum absorption wavelength of the coating film were measured. Further, the base color was stored at room temperature for one month, and the change in its viscosity was measured.
The results are shown in Table 4.

[0062]

Example 21 (Preparation and Evaluation of Paint) In order to confirm the effect of surface treatment of a normal (non-sulfonated) pigment with a sulfonated pigment, a paint was prepared according to the following formulation. -Red pigment composition obtained in Example 6 50 parts-Xylene 50 parts-Alkyd resin (* 1) 100 parts-Dispersant (* 2) 5 parts (Note) (* 1) Hitachi Chemical Co., Ltd., palm Short oil alkyd resin (* 2) Sols Perth 24000GR (polyester dispersant manufactured by Zeneca)

30% of the above-mentioned compounding ingredients with a high-speed disper
After mixing for 1 minute and the resulting blended solution for 1 hour on a small sand mill, the above alkyd resin (solid content 50%)
And 367 parts of melamine resin (200 parts of butylated melamine resin manufactured by Dainippon Ink and Chemicals, Inc., solid content 60%) were additionally compounded, and further kneaded for 10 minutes. An alkyd resin / melamine resin ratio of resin solids was 7/3 (mass ratio), and a paint of primary color formulation-1 having a pigment concentration of 15% with respect to the resin solids was prepared.

The above-prepared coating composition was prepared by first measuring the viscosity value at a rotor rotation speed of 6 rpm with a B-type viscometer in the final coating composition and then measuring the viscosity value at a rotor rotation speed of 60 rpm to prepare the primary color mixture-1. The viscous behavior of Also, this final primary color enamel was spread on the surface-coated paper with a 6 mil applicator. After allowing the color-developed paper to stand at room temperature for 1 hour, the color-developed coating film was heat-cured at 140 ° C. for 30 minutes in an oven. The dispersibility of the pigment was evaluated by measuring the gloss of the developed product. The results are shown in Table 5.

For comparison, the non-sulfonated red pigment PR-254 was used instead of the red pigment composition used in Example 21.
The same operation as in Example 21 was performed except that was used. Then, color development was performed in the same manner as in Example 21, and the gloss of this color development product was measured to evaluate the dispersibility of the pigment. The results are shown in Table 5.

Example 22 (Preparation and Evaluation of Paint) In order to confirm the surface treatment effect of the pigment, a paint was prepared according to the following formulation. Red pigment (PR-254) 47.5 parts Pigment composition of Example 7 2.5 parts Mixed thinner (* 3) 50.0 parts Acrylic polyol resin (* 4) 100.0 parts (* 3) ) Mixed thinner: toluene / butyl acetate = 6/4
(Mass ratio) (* 4) Acrydic A-801 manufactured by Dainippon Ink and Chemicals, Inc.

The above-mentioned compounding ingredients were mixed with a high speed disperser 30
The resulting blended product was mixed for 1 hour with a small sand mill, and then the above acrylic polyol resin (solid content 5
0%) was added to 400 parts, and finish kneading was performed for 10 minutes. A paint of primary color formulation-2 was prepared in which the pigment mass content was 20% with respect to the acrylic polyol resin solid content.

Further, after adding an equivalent amount of isocyanate as a curing agent to the enamel of this final primary color formulation-2 and blending it,
Color was applied to the surface coated paper with a 6 mil applicator.
The spread paper was left at room temperature for 24 hours to cure the coating film. The dispersibility of the pigment was evaluated by measuring the gloss of the developed product. The results are shown in Table 5.

For comparison, in Example 22, the pigment composition of Example 7 was not used, and the non-sulfonated red pigment PR was used.
The same operation as in Example 21 was performed except that only -254 was used. Then, color development was performed in the same manner as in Example 21, and the gloss of this color development product was measured to evaluate the dispersibility of the pigment. The results are shown in Table 5.

Example 23 (Synthesis of amine salt) While dispersing 100 parts of an aqueous paste of the phthalocyanine blue pigment composition obtained in Example 10 (pigment content 25%) in water, an aqueous solution of stearylamine in acetic acid was added. Three
The pH was adjusted to about 10 with a 0% aqueous sodium hydroxide solution, and the sulfonated pigment was used as a stearylamine salt. Thus, 27.3 g of a phthalocyanine blue pigment composition was obtained.

The respective components were mixed and dispersed sufficiently uniformly according to the following formulation to obtain a room-temperature quick-drying blue quick-drying enamel for metal materials such as machines and vehicles. When this coating material was applied to the substrate, a clear and beautiful coating was performed. -The phthalocyanine blue pigment composition obtained above 5.4 parts-R-titanium white 2.0 parts-Quick-drying styrenated alkyd resin 72.6 parts-Xylol 6.6 parts-Mineral spirit 13.0 parts-6 % Cobalt Naphthenate 0.3 parts / Anti-skin agent 0.1 parts

Example 24 (Synthesis of amine salt) 100 parts of water paste of the aluminum phthalocyanine blue pigment composition obtained in Example 11 (pigment content 32.1).
%) In water, add an aqueous solution of stearylamine in acetic acid, and add p with 30% aqueous sodium hydroxide solution.
The H was adjusted to about 10 to make the sulfonated pigment a stearyl amine salt. Thus, 32.9 parts of a phthalocyanine blue pigment composition was obtained.

(Plastic molded article) 5 parts of a finely pulverized product of the above aluminum phthalocyanine blue pigment composition was
The molded product, which was mixed with 1,000 parts of polyethylene and injection-molded at 250 ° C., was colored in a uniform blue color.

Example 25 (Preparation of anionic granular polymer and charged mosaic membrane and evaluation of desalination performance) -Styrene 41.6 parts-Acrylonitrile 7.1 parts-Hydroxyethyl methacrylate 8.1 parts-Divinylbenzene 8. 7 parts / potassium persulfate 0.5 parts / water 1,000 parts The above ingredients were charged into a flask and placed at 80 ° C. under a nitrogen stream for 8 hours.
Polymerized for hours. The average particle size of the obtained polymer is about 18
It was 0 nm.

100 parts of a white polymer obtained by filtering, drying and pulverizing the above granular polymer was dried at 105 ° C. in a dryer.
It was pre-dried for 1 hour, placed in a 1-liter flask, and sulfur trioxide gas heated to 80 to 110 ° C. was introduced so as to have a concentration of 8% with respect to air and reacted for 3 hours. Then, the granular polymer was dispersed in 2 liters of water, neutralized with sodium carbonate, filtered, and thoroughly washed with water. The obtained anionic granular polymer was analyzed by infrared absorption spectrum and ion chromatography.
It was confirmed that almost one sulfone group was introduced into the aromatic ring. This was designated as a cationic microgel.

Based on the description of JP-A-2000-309654, a granular substance of a chloromethylstyrene: divinylbenzene (20: 1) cross-linked copolymer is reacted with triethylamine to form a quaternary ammonium salt, and a cationic microgel is prepared. And 3.0 of the above cationic microgel
Parts, 7.0 parts of the anionic microgel described above, 10 parts of a hydrogenated product of acrylonitrile-butadiene resin, and 80 parts of N, N-dimethylformamide were prepared. The above coating film is coated on a polypropylene resin-coated release paper with a knife coater to a dry film thickness of about 30 μm, and a polypropylene nonwoven fabric is adhered onto it, dried with hot air, and post-treated such as washing to perform nonwoven fabric. A support reinforced charged mosaic membrane was obtained.

According to the method disclosed in the above publication, an aqueous solution of potassium chloride and glucose was used as a stock solution, deionized water was put in a dialysis water tank, and dialysis was performed under normal pressure. Potassium chloride was dialyzed in the dialysate, and glucose was hardly dialyzed, and a result showing good separation performance was obtained.

[0079]

According to the present invention described above, solid particles, that is, organic pigments, carbon black pigments, carbon black, resin fine particles and the like are obtained by catalytic oxidation of sulfur dioxide gas produced by burning sulfur. Sulfonated solid particles capable of selecting sulfur trioxide gas as it is or by mixing it with an inert gas, in a solid phase-gas phase reaction, industrially safe, and easily at low cost, particularly in a high range of sulfonation degree A method of manufacturing the same is provided. The composition thus obtained is used in the conventionally known applications. In particular, the pigment composition is not only used as a colorant for ordinary paints and printing inks, but also as an easily dispersible pigment composition suitable as a colorant for inkjet inks and CFs, and as a pigment dispersant or dispersion aid. Can also be used as

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hisao Okamoto             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. (72) Inventor Atsushi Nogami             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. (72) Inventor Naoyuki Sakai             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. (72) Inventor Hideyuki Koiso             1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Large             Within Nissei Chemical Co., Ltd. F-term (reference) 2C056 FC02                 2H086 BA55                 4J037 AA02 EE08 EE28                 4J039 BA04 BE01 GA24

Claims (16)

[Claims] 1. A sulfur-oxide gas obtained by catalytically oxidizing a sulfur dioxide gas produced by burning sulfur with powdery and / or granular solid particles in a dry state is used to form a gas phase-solid. A method for producing sulfonated solid particles, which comprises sulfonation in a phase state. 2. The method for producing sulfonated solid particles according to claim 1, wherein the sulfur trioxide gas is used as a mixture with the sulfur trioxide and a gas inert to the solid particles. 3. The solid particles are at least one selected from the group consisting of organic pigments, carbon black pigments, conductive carbon blacks, carbon blacks for batteries, carbon blacks for rubbers, water-insoluble dyes, and resin fine particles. The method for producing sulfonated solid particles according to claim 1. 4. The solid particles are carbon black pigment, conductive carbon black, carbon black for batteries, carbon black for rubber, and their sulfonation degree (sulfone group per unit mass of solid particles: —SO ₃ H). amount)
Is 1 to 10% by mass, the method for producing sulfonated solid particles according to claim 1. 5. The solid particles are organic pigments, water-insoluble dyes and resin fine particles, and their sulfonation degree is 0.1.
It is -30 mass%, The manufacturing method of the sulfonated solid particle of Claim 1. 6. A method for producing sulfonated solid particles containing a sulfonate, which comprises neutralizing the sulfonated solid particles obtained by the method according to claim 1 with a basic compound. 7. Sulfonated solid particles produced by the method according to any one of claims 1 to 6. 8. A composition comprising sulfonated solid particles, characterized in that the sulfonated solid particles according to claim 7 are dispersed alone or together with other solid particles in a medium. 9. A coloring composition, wherein the sulfonated solid particles according to claim 7 are sulfonated pigments, and the sulfonated pigments are dispersed in a medium. 10. A coloring composition, wherein the sulfonated solid particles according to claim 7 are sulfonated pigments, and the sulfonated pigments are contained as a dispersant for the pigments. 11. The coloring composition according to claim 9, wherein the medium is an aqueous medium and the dispersion is an aqueous pigment ink. 12. An image recording method comprising using the coloring composition according to claim 9 as an image recording agent. 13. An image display method, comprising using the coloring composition according to claim 9 as an image display material. 14. The image recording method according to claim 12, wherein the image recording agent according to claim 12 is an inkjet ink or an electrodeposition recording liquid, and the image recording method is an inkjet recording method or an electrodeposition recording method. . 15. An image recording apparatus comprising the image recording agent according to claim 14. 16. An ink jet printer comprising the image recording agent according to claim 14.